Alkylene oxides are known for a multiplicity of utilities. Ethylene oxide, for example, is used to produce ethylene glycol, nonionic surfactants, glycol ethers, ethanolamines, and polyethylene polyether polyols. Ethylene glycol is used as an automotive coolant, as antifreeze, and in preparing polyester fibers and resins. Propylene oxide is used to produce propylene glycol and polypropylene polyether polyols, which are used in polyurethane polymer applications.
The production of alkylene oxides via catalytic epoxidation of olefins in the presence of oxygen using silver based catalysts is known. Conventional silver-based catalysts used in such processes typically provide a relatively lower efficiency or “selectivity” (i.e., a lower percentage of the reacted alkylene is converted to the desired alkylene oxide). In certain exemplary processes, when using conventional catalysts in the epoxidation of ethylene, the theoretically maximal efficiency towards ethylene oxide, expressed as a fraction of the ethylene converted, does not reach values above the 6/7 or 85.7 percent limit. Therefore, this limit had long been considered to be the theoretically maximal efficiency of this reaction, based on the stoichiometry of the following reaction equation:7C2H4+6O2→6C2H4O+2CO2+2H2O
cf. Kirk-Othmer's Encyclopedia of Chemical Technology, 4th ed., Vol. No. 9, 1994, p. 926.
Certain “high efficiency” or “high selectivity” modern silver-based catalysts are highly selective towards alkylene oxide production. For example, when using certain modern catalysts in the epoxidation of ethylene, the theoretically maximal efficiency towards ethylene oxide can reach values above the 6/7 or 85.7 percent limit referred to, for example 88 percent, or 89 percent, or above. As used herein, the terms “high efficiency catalyst” and “high selectivity catalyst” refer to a catalyst that is capable of producing an alkylene oxide from the corresponding alkylene and oxygen at an efficiency greater than 85.7 percent. The observed actual efficiency of a high efficiency catalyst may fall below 85.7 percent under certain conditions based on process variables, catalyst age, etc. However, if the catalyst is capable of achieving at least an 85.7 percent efficiency, at any point during its life, for example, under any set of reaction conditions as described in the Examples hereinafter, or by extrapolating lower efficiencies observed at two different oxygen conversions obtained by varying gas hourly space velocity to the limiting case of zero oxygen conversion, it is considered to be a high efficiency catalyst. Such highly efficient catalysts, which may comprise as their active components silver, rhenium, at least one further metal, and optionally, a rhenium co-promoter, are disclosed in EP0352850B1 and in several subsequent patent publications. “Promoters,” sometimes referred to as “inhibitors” or “moderators,” refer to materials that enhance the performance of the catalysts by either increasing the rate towards the desired formation of alkylene oxide and/or suppressing the undesirable oxidation of olefin or alkylene oxide to carbon dioxide and water, relative to the desired formation of alkylene oxide. As used herein, the term “co-promoter” refers to a material that—when combined with a promoter—increases the promoting effect of the promoter. In addition, promoters may also be referred to as “dopants.” In the case of those promoters that provide high efficiencies, the terms “high efficiency dopants” or “high selectivity dopants” may be used.
“Promoters” can be materials that are introduced to catalysts during the preparation of the catalysts (solid phase promoters). In addition, “promoters” can also be gaseous materials that are introduced to the epoxidation reactor feed (gas phase promoters). In one example, an organic halide gas phase promoter may be added continuously to the epoxidation reactor feed to increase the catalyst efficiency. For silver-based ethylene epoxidation catalysts, both solid and gas phase promoters are typically required in any commercial processes.
All silver based catalysts used in alkylene oxide production processes are subject to an aging-related performance decline during normal operation, and they need to be exchanged periodically. The aging manifests itself by a reduction in the activity of the catalyst and may also manifest itself by a reduction in efficiency. Usually, when a reduction in catalyst activity occurs, the reaction temperature is increased in order to maintain a constant alkylene oxide production rate. The reaction temperature may be increased until it reaches the design limit or becomes undesirably high, or the efficiency may become undesirably low, at which point in time the catalyst is deemed to be at the end of its lifetime and would need to be exchanged or regenerated. Current industry practice is to discharge and replace the catalyst when it is at the end of its useful life. The silver is recovered and promoters may be recovered from the discharged catalyst.
Conventional catalysts have relatively flat efficiency curves with respect to the gas phase promoter concentration in the feed, i.e., the efficiency is almost invariant (i.e., the change in efficiency with respect to a change in gas phase promoter concentration in the feed is less than about 0.1%/ppmv) over a wide range of promoter concentrations, and this invariance is substantially unaltered as reaction temperature is changed during prolonged operation of the catalyst. However, conventional catalysts have nearly linear activity decline curves with respect to the gas phase promoter concentration in the feed, i.e., with increasing gas phase promoter concentration in the feed, temperature has to be increased or the alkylene oxide production rate will be reduced. Therefore, when using a conventional catalyst, for optimum efficiency, the gas phase promoter concentration in the feed can be chosen at a level at which the maximum efficiency can be maintained at relatively lower operating temperatures. Typically, the gas phase promoter concentration can remain substantially the same during the entire lifetime of a conventional catalyst. On the other hand, the reaction temperature may be adjusted to obtain a desired production rate without any substantial impact on efficiency due to non-optimal gas phase promoter concentration.
By contrast, high efficiency catalysts tend to exhibit relatively steep efficiency curves as a function of gas phase promoter concentration as the concentration moves away from the value that provides the highest efficiency (i.e., the change in efficiency with respect to a change in gas phase promoter concentration is at least about 0.2%/ppmv when operating away from the efficiency maximizing promoter concentration). Thus, small changes in the promoter concentration can result in significant efficiency changes, and the efficiency exhibits a pronounced maximum, i.e. an optimum, at certain concentrations (or feed rates) of the gas phase promoter, when reactor pressure and feed gas composition are kept unchanged for a given reaction temperature and catalyst age. Moreover, the efficiency curves and the optimum gas phase promoter concentration tend to be strong functions of reaction temperature and are thus significantly affected if reaction temperature is varied, for example, to compensate for decreases in catalyst activity (i.e., the change in efficiency with respect to a change in reaction temperature can be at least about 0.1%/° C. when operating away from the efficiency maximizing promoter concentrations for the selected temperatures). In addition, rhenium-promoted high efficiency catalysts have exhibited significant activity increases with increases in the gas phase promoter concentration in the feed, i.e., with increasing gas phase promoter concentration in the feed, temperature has to be decreased or the production rate will increase. Thus, for conventional catalysts, the rate of alkylene oxide production is typically controlled by adjusting reaction temperature, while for high efficiency catalysts gas phase promoter concentration and/or reaction temperature may be adjusted to control the rate.
To address the strong influence of reaction temperature and gas phase promoter concentration on the efficiency of high efficiency catalysts, it has been proposed to use the temperature differential to first calculate the new gas phase promoter concentration. The gas phase promoter concentration changes are made whenever the reaction temperature is changed (U.S. Pat. No. 7,193,094; European Patent No. 1,458,699). However, this technique increases the complexity of the process and the controls that are required for automated operation. It can also result in excessive or insufficient gas phase promoter consumption and increase the sensitivity of the process to disturbances in reaction temperature. It also requires knowledge of a mathematical relationship between temperature and efficiency, which may be difficult or costly to obtain. Finally, this method only takes into account the variation in optimum promoter concentration with temperature and does not take into account the fact that the optimum promoter concentration can also be a function of other process variables such as catalyst age. Thus, a need has arisen for a process that addresses the foregoing issues.